C. Cimarelli et al. / Tetrahedron: Asymmetry 20 (2009) 2234–2239
2239
NMR (100 MHz, CDCl3): d 21.7, 25.9, 26.2, 29.9, 34.7, 38.0, 58.7,
72.1, 109.4, 149.1. Anal. Calcd for C20H35NO2 (321.50): C, 74.72;
H, 10.97; N, 4.36. Found: C, 74.86; H, 11.12; N, 4.11.
4.15.1. 1,2-((1R,2R,4S)-1-Methyl-4-(prop-1-en-2-yl)cyclohexyldi
amino)-N1,N2-diethyl-phosphonate 15
Yellow oil ; ½a 2D0
ꢂ
¼ ꢀ20:5 (c 0.6, CHCl3); IR (liquid film): mmax
3436, 1445, 1392, 1237, 1098, 1028, 962 cmꢀ1
;
1H NMR
4.13. Preparation of diethyl 2-((1R,2R,5S)-2-hydroxy-2-methyl-
5-(prop-1-en-2-yl)cyclohexylamino)ethylphosphonate 13
(400 MHz, CDCl3): d 1.05 (s, 3H), 1.30 (t, 12H, J = 6.8 Hz), 1.43–
1.58 (m, 5H), 1.71 (s, 3H), 1.83–2.04 (m, 7H), 2.13–2.21 (m, 1H),
2.49 (dd, 1H, J = 6.0, 3.2 Hz), 2.67–2.85 (m, 3H), 3.00 (ddt, 1H,
J = 14.5, 12.0, 7.3 Hz), 4.05–4.16 (m, 8H), 4.71–4.76 (m, 2H); 13C
NMR (100 MHz, CDCl3): d 16.5, 16.7, 21.6, 22.0, 25.8, 26.3, 28.5,
29.1, 29.8, 32.0, 35.1, 35.2, 38.0, 42.1, 42.2, 55.4, 59.8, 61.6, 61.7,
109.2, 149.2; MS (API-ES) m/z: 497.2 (MH+, 100), 498.2 (26),
519.2 (MNa+). Anal. Calcd for C22H46N2O6P2 (496.56): C, 53.21; H,
9.34; N, 5.64. Found: C, 52.98; H, 9.46; N, 5.41.
To a solution of trans-aminoalcohol 10 (0.50 g, 2.96 mmol) in
ethanol (3 mL) was added diethyl vinylphosphonate (0.49 g,
3.00 mmol). The mixture was heated at reflux for 15 h. then was
cooled until room temperature and the solvent was evaporated un-
der reduced pressure. The product was purified by column chro-
matography with EtOH/AcOEt, 1:1 mixture as eluent giving 13 as
colourless oil (0.86 g, 2.60 mmol, Y = 88%).
Acknowledgements
4.13.1. Diethyl 2-((1R,2R,5S)-2-hydroxy-2-methyl-5-(prop-1-
en-2-yl)cyclohexylamino) ethylphosphonate 13
Colourless oil; ½a D20
ꢂ
¼ ꢀ28:0 (c 1.1, CHCl3); IR (Nujol): mmax
The financial support of this research by a grant from University
of Camerino and from MIUR-PRIN is gratefully acknowledged.
3411, 1455, 1228, 1099, 962 cmꢀ1
;
1H NMR (400 MHz, CDCl3): d
1.05 (s, 3H), 1.18 (t, 6H, J = 7.1 Hz), 1.32–1.60 (m, 5H), 1.58 (s,
3H), 1.79 (t, 2H, J = 6.8 Hz), 1.84 (t, 2H, J = 6.8 Hz), 2.05 (br m,
1H), 2.39 (dd, 1H, J = 6.0, 3.4 Hz), 2.63 (ddt, 1H, J = 18.8, 12.0,
6.0 Hz), 2.66 (br s, 1H), 2.90 (ddt, 1H, J = 15.4, 12.0, 6.8 Hz), 3.89–
4.03 (m, 4H), 4.52 (br s, 2H); 13C NMR (100 MHz, CDCl3): d 16.3,
16.4, 21.3, 25.4, 25.5, 26.1, 28.2, 30.2, 34.5, 37.8, 41.7, 61.4, 61.5,
71.6, 109.1, 148.8. Anal. Calcd for C16H32NO4P (333.4): C, 57.64;
H, 9.67; N, 4.20. Found: C, 57.69; H, 9.51; N, 4.04.
References
1. (a) Fache, F.; Schulz, E.; Tommassino, M. L.; Lemaire, M. Chem. Rev. 2000, 100,
2159–2232; (b) Lucet, D.; Le Gall, T.; Mioskowski, C. Angew. Chem., Int. Ed. 1998,
37, 2580–2627; (c) Bennani, Y. L.; Hanessian, S. Chem. Rev. 1997, 97, 3161–
3196; (d) Togni, A.; Venanzi, L. M. Angew. Chem., Int. Ed. 1994, 33, 497–526; (e)
Yang, Y.-Q.; Zhao, G. Chem. Eur. J. 2008, 14, 10888–10891; (f) Rasappan, R.;
Reiser, O. Eur. J. Org. Chem. 2009, 1305–1308; (g) Amoroso, D.; Graham, T. W.;
Rongwei, G.; Tsang, C.-W.; Kamaluddin, A.-R. Aldrichim. Acta 2008, 41, 15–26.
2. (a) Paquette, L. A.; Kang, H.-J. J. Am. Chem. Soc. 1991, 113, 2610–2621; (b)
Baudouy, R.; Prince, P. Tetrahedron 1989, 45, 2067–2074; (c) Marron, B. E.;
Nicolaou, K. C. Synthesis 1989, 537–541; (d) Tius, M. A.; Kerr, M. A. Synth.
Commun. 1988, 18, 1905–1911; (e) Baker, R.; Borges, M.; Cooke, N. G.; Herbert,
R. H. J. Chem. Soc., Chem. Commun. 1987, 414–416; (f) Mori, K.; Kato, M.
Tetrahedron Lett. 1986, 27, 981–982; (g) Ła˛czkowsky, K. Z.; Kmieciak, A.;
4.14. Preparation of diethyl 2-((1R,2R,5S)-2-amino-2-methyl-5-
(prop-1-en-2-yl)cyclohexylamino) ethylphosphonate 14
Product 14 was prepared starting from trans-diaminolimonene
8 (0.50 g, 2.97 mmol), according to the procedure followed for
product 13 (0.89 g, 2.67 mmol, 90%).
Kozakiewicz,
A.
Tetrahedron:
Asymmetry
2009.
3. (a) Watts, C. C.; Thoniyot, P.; Hirayama, L. C.; Romano, T.; Singaram, B.
Tetrahedron: Asymmetry 2005, 16, 1829–1835; (b) Steiner, D.; Sethofer, S. G.;
Goralski, C. T.; Singaram, B. Tetrahedron: Asymmetry 2002, 13, 1477–1483; (c)
Xu, Q.; Wu, X.; Pan, X.; Chan, A. C. S.; Yang, T.-K. Chirality 2002, 14, 28–31; (d)
Pu, L.; Hong-Bin, Y. Chem. Rev. 2001, 101, 757–824; (e) Noyori, R. Asymmetric
Catalysis in Organic Synthesis; Wiley: New York, 1994; (f) Steiner, D.; Ivison, L.;
Goralski, C. T.; Appel, R. B.; Gojkovic, J. R.; Singaram, B. Tetrahedron: Asymmetry
2002, 13, 2359–2363; (g) Andrews, P. C.; Blair, M.; Fraser, B. H.; Junk, P. C.;
Massi, M.; Tuck, L. Tetrahedron: Asymmetry 2006, 17, 2833–2838.
4. (a) Royals, E. E.; Leffingwell, J. C. J. Org. Chem. 1966, 31, 1937–1944; (b)
Newhall, W. F. J. Org. Chem. 1964, 29, 185–187.
5. Alcaraz, L.; Cridl, A.; Kinchin, E. Org. Lett. 2001, 3, 4051–4053.
6. Royals, E. E.; Leffingwell, J. C. Tetrahedron Lett. 1965, 43, 3829–3837.
7. (a) Sommerdijk, N. A. J. M.; Buynsters, P. J. J. A.; Akdemir, H.; Geurts, D. G.;
Nolte, R. J. M.; Zwanenburg, B. J. Org. Chem. 1997, 62, 4955–4960; (b) Gololobov,
Y. G.; Zhmurova, I. N.; Kasukhin, L. F. Tetrahedron 1981, 37, 437–472.
8. Voronkov, M. V.; Gontcharov, A. V.; Kanamarlapudi, R. C.; Richardson, P. F.;
Wang, Z.-M. Org. Proc. Res. Dev. 2005, 9, 221–224.
4.14.1. Diethyl 2-((1R,2R,5S)-2-amino-2-methyl-5-(prop-1-en-
2-yl)cyclohexylamino) ethylphosphonate 14
Yellow oil; ½a 2D0
ꢂ
¼ ꢀ24:0 (c 0.7, CHCl3); IR (liquid film): mmax
3435, 1642, 1454, 1226, 1055, 1028, 962 cmꢀ1
;
1H NMR
(400 MHz, CDCl3): d 1.03 (s, 3H), 1.27 (t, 6H, J = 7.3 Hz), 1.42–
1.68 (m, 8H), 1.68 (s, 3H), 1.78 (ddd, 1H, J = 12.8, 9.8, 3.0 Hz),
1.89 (t, 1H, J = 7.3 Hz), 1.93 (t, 1H, J = 7.3 Hz), 2.11–2.21 (m, 1H),
2.33 (dd, 1H, J = 5.6, 3.2 Hz), 2.70 (ddt, 1H, J = 16.7, 12.0, 7.3 Hz),
2.97 (ddt, 1H, J = 15.4, 12.0, 7.3 Hz), 3.98–4.12 (m, 4H), 4.68–4.73
(m, 2H); 13C NMR (100 MHz, CDCl3): d 16.5, 16.6, 21.7, 26.2, 27.5,
30.1, 35.7, 37.8, 37.9, 41.9, 42.0, 51.9, 61.7, 62.6, 109.3, 148.9. Anal.
Calcd for C16H33N2O3P (332.42): C, 57.81; H, 10.01; N, 8.43. Found:
C, 57.63; H, 10.21; N, 8.21.
9. Voronkov, M. V.; Kanamarlapudi, R. C.; Richardson, P. Tetrahedron Lett. 2005,
46, 6907–6910.
10. (a) Brown, H. C.; Suzuki, A. J. Am. Chem. Soc. 1967, 89, 1933–1941; (b) Watts, C.
C.; Thoniyot, P.; Cappuccio, F.; Verhagen, J.; Gallagher, B.; Singaram, B.
Tetrahedron: Asymmetry 2006, 17, 1301–1307.
4.15. Preparation of tetraethyl 1,2-((1R,2R,4S)-1-methyl-4-(pro
p-1-en-2-yl)cyclohexyldiamino)-N1,N2-diethyl-phosphonate 15
11. Spartan0 06, Wavefunction, Inc., Irvine, CA.
12. Partal Ureña, F.; Avilés Moreno, J. R.; López González, J. J. Tetrahedron:
Asymmetry 2009, 20, 89–97.
13. (a) Uenishi, J.; Hamada, M. Tetrahedron: Asymmetry 2001, 12, 2999–3006; (b)
Noyori, R. Asymmetric Catalysis in Organic Synthesis;; John Wiley and Sons: New
York, 1994.
Product 15 was prepared according to the procedure followed
for product 14, starting from trans-diaminolimonene 8 (0.50 g,
2.97 mmol) and using 6 mmol of diethyl vinylphosphonate, and
stirring for 70 h. (0.93 g, 1.87 mmol, 63%).